CN111389448A - Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material - Google Patents
Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material Download PDFInfo
- Publication number
- CN111389448A CN111389448A CN202010372279.1A CN202010372279A CN111389448A CN 111389448 A CN111389448 A CN 111389448A CN 202010372279 A CN202010372279 A CN 202010372279A CN 111389448 A CN111389448 A CN 111389448A
- Authority
- CN
- China
- Prior art keywords
- solution
- precursor
- wood
- soaking
- batten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims description 37
- 230000001699 photocatalysis Effects 0.000 title description 9
- 239000002243 precursor Substances 0.000 claims abstract description 139
- 239000002023 wood Substances 0.000 claims abstract description 129
- 239000000243 solution Substances 0.000 claims abstract description 125
- 238000003756 stirring Methods 0.000 claims abstract description 107
- 238000002791 soaking Methods 0.000 claims abstract description 106
- 238000001035 drying Methods 0.000 claims abstract description 56
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 41
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012670 alkaline solution Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 238000005520 cutting process Methods 0.000 claims abstract description 25
- 238000010000 carbonizing Methods 0.000 claims abstract description 24
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 24
- 231100000719 pollutant Toxicity 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000003929 acidic solution Substances 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 67
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- 238000003763 carbonization Methods 0.000 claims description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000009656 pre-carbonization Methods 0.000 claims description 30
- 229920000877 Melamine resin Polymers 0.000 claims description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 241000219071 Malvaceae Species 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000006748 scratching Methods 0.000 claims description 11
- 230000002393 scratching effect Effects 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012495 reaction gas Substances 0.000 claims description 10
- 208000028659 discharge Diseases 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 241000208140 Acer Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241000167854 Bourreria succulenta Species 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 235000019693 cherries Nutrition 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000003698 laser cutting Methods 0.000 claims description 2
- 238000000352 supercritical drying Methods 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 20
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 20
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000001782 photodegradation Methods 0.000 abstract description 3
- 239000010875 treated wood Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a graded porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps: selecting waste natural wood, removing surface pollutants, and cutting the waste natural wood into battens; repeatedly washing the battens, stirring and soaking the battens in an acidic or alkaline solution, and drying to obtain a batten precursor; stirring and soaking the batten precursor in a nitrogen-containing precursor solution, and then taking out and drying; repeating the soaking and drying processes until white particles are uniformly attached to the surface of the batten precursor; pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the third step, finally carbonizing, cooling to room temperature, and taking out the solid, namely the graded porous g-C for photocatalytic degradation3N4@ wood composite material. g-C of the invention3N4The @ wood composite material has high photodegradation efficiency on methylene blue, and the efficiency can still reach more than 80 percent after 5 times of recycling.
Description
Technical Field
The invention relates to a preparation method of a composite material, in particular to a hierarchical porous g-C for photocatalytic degradation3N4A preparation method of a @ wood composite material.
Background
The preparation of functional materials with ordered hierarchical porous structures from bottom to top and the corresponding application scale can be achieved, which is one of the major challenges in the field of material science and engineering. Manufacturing methods based on self-assembly processes have made significant advances in centimeter-scale dimensions. However, the development of materials with ordered pore structures on the micro-nano scale remains a difficult task. Fortunately, natural wood has been proven to have a multi-layer porous structure of micro-nano scale, which is very suitable for micro-nano technical processing by surface modification or functionalization. From the advantage, the wood can be further developed into a functional material through chemical modification, and the application field of the wood is expanded.
g-C3N4Is a typical polymer semiconductor with the structure having C, N atoms in sp2Hybridization results in the formation of highly delocalized pi-conjugated systems. The preparation method has the characteristics of visible light correspondence, adjustable band gap width, low preparation cost, environmental friendliness and the like. If wood is mixed with g-C3N4The star material can be used for sewage treatment by carrying out chemical combination and keeping the natural ordered pore structure of the wood. It has the following unique advantages: (1) compared with a manual ordered structure, the wood structure has the advantages of wider pore size distribution, wider ordered degree range, lower manufacturing cost and more stable structure and mechanical strength; (2) the large specific surface area and the ordered porous structure reduce the time for adsorbing pollutants in the first stage of photocatalytic degradation, and improve the overall photocatalytic efficiency; (3) the continuous and rapid adsorption action provides continuous working opportunities for the second stage of photocatalytic degradation, further improves the photocatalytic efficiency, and improves the recycling times of samples; (4) g-C3N4With visible lightIn response, the photocatalyst can be directly used as a photocatalytic activity center without complicated chemical treatment.
Based on the above inspiration, the invention adopts a relatively simple method to prepare the g-C with the micro-nano ordered interconnected hierarchical porous structure3N4@ Wood composite Material, wherein g-C3N4Evenly distributed on the inner and outer surfaces of the wood. The invention lays a foundation for preparing functional integrated materials such as adsorption, photocatalysis, environmental remediation and the like by utilizing the natural structure of the wood.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the purpose of the invention, a graded porous g-C for photocatalytic degradation is provided3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting waste natural wood, removing surface pollutants, and cutting the waste natural wood into battens;
repeatedly washing the batten, stirring and soaking the batten in an acidic or alkaline solution, and drying to obtain a batten precursor;
step three, stirring and soaking the batten precursor in a nitrogen-containing precursor solution, and then taking out and drying the batten precursor; repeating the soaking and drying processes for 3-5 times until white particles are uniformly attached to the surface of the batten precursor;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, then finally carbonizing, cooling to room temperature, and taking out solids, namely the graded porous g-C for photocatalytic degradation3N4@ wood composite material.
Preferably, the waste natural wood includes, but is not limited to, any one of basswood, bamboo, walnut, sapelli wood, cherry wood, and maple wood; in the first step, the method for removing the surface pollutants comprises one or a combination of more of surface scratching, water washing, ethanol washing, acid washing and alkali washing; the cutting method is any one of hand saw, electric saw, laser cutting and electric cutting; the shape of the wood strip is any one of square, rectangle, sphere and ellipse; the acid washing adopts one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid and silicic acid as a reagent; the alkaline washing reagent is one or a combination of sodium hydroxide, potassium hydroxide, ammonia water and ammonia monohydrate; the drying mode is as follows: natural air drying, freeze drying, supercritical drying, constant temperature heating drying, and variable temperature heating drying.
Preferably, in the second step, the acidic solution is one or a mixture of more of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, an acetic acid solution, a carbonic acid solution and a silicic acid solution, the alkaline solution is one or a combination of more of a sodium hydroxide solution, a potassium hydroxide solution, an ammonia water solution and an ammonia monohydrate solution, the concentration of the acidic solution is 0.5-1.5 mol/L, the concentration of the alkaline solution is 0.5-1.5 mol/L, the stirring and soaking time in the acidic or alkaline solution is 3-5 days, and the stirring speed of the stirring and soaking is 300-400 r/min.
Preferably, in the second step, the consumption of the wood strips is that 5-10 wood strips with the size of 3x2x1cm are added into 500m of L acidic solution or alkaline solution.
Preferably, the nitrogen-containing precursor solution is any one of a melamine solution, a urea solution and a thiourea solution, the mass fraction of the nitrogen-containing precursor solution is 0.1-20 wt%, the temperature for stirring and soaking in the nitrogen-containing precursor solution is 10-100 ℃, the time for stirring and soaking is 0.1-3 h, the stirring speed for stirring and soaking is 300-400 r/min, and the amount of the wood strip precursor is that 1-2 wood strip precursors with the size of 3x2x1cm are added into every 200m L of the nitrogen-containing precursor solution.
Preferably, the pre-carbonization and the final carbonization are carried out in an atmosphere furnace, the atmosphere furnace is any one of a vertical furnace, a horizontal furnace and a tubular furnace, the gas adopted by the atmosphere furnace is inert gas and/or nitrogen-containing gas, the pre-carbonization temperature is 100-400 ℃, the pre-carbonization time is 0.1-5 h, the gas flow rate is 1-200 m L/min, the final carbonization temperature is 400-800 ℃, the final carbonization time is 0.1-30 h, and the gas flow rate is 1-200 m L/min.
Preferably, in the fourth step, the batten precursor with white particles uniformly attached to the surface, obtained in the third step, is directly carbonized, cooled to room temperature, and the solid, namely the graded porous g-C for photocatalytic degradation is taken out3N4The method comprises the following steps of @ wood composite material, wherein direct carbonization is carried out in an atmosphere furnace, the atmosphere furnace is any one of a vertical furnace, a horizontal furnace and a tubular furnace, gas adopted by the atmosphere furnace is inert gas and/or nitrogen-containing gas, the direct carbonization temperature is 400-800 ℃, the time is 1-30 hours, and the gas flow rate is 1-200 m L/min.
Preferably, the inert gas is any one of argon and nitrogen; the nitrogen-containing gas is ammonia gas.
Preferably, the second step further comprises the following steps: putting the batten precursor into a supercritical device, soaking for 10-30 min in a supercritical acetone-water system with the temperature of 350-370 ℃ and the pressure of 10-15 MPa, and drying to obtain a treated batten precursor; and placing the treated batten precursor into a reaction cavity of low-temperature plasma, vacuumizing until the pressure in the cavity is stable, introducing reaction gas containing ammonia, and performing surface treatment on the batten precursor through low-temperature plasma discharge to obtain the treated batten precursor.
Preferably, the volume ratio of acetone to water in the supercritical acetone-water system is 4: 1; the reaction gas containing ammonia gas is ammonia gas or mixed gas of ammonia gas and argon gas, the power during low-temperature plasma discharge treatment is 30-100W, the pressure is 15-25 Pa, and the time is 5-8 min.
The invention at least comprises the following beneficial effects: the invention prepares the g-C with the micro-nano ordered interconnection hierarchical porous structure3N4@ Wood composite Material, wherein g-C3N4Uniformly distributed on the inner and outer surfaces of the wood; the preservation of the pore structure of the natural wood is proved by a scanning electron microscope and a nitrogen adsorption/desorption isotherm; characterization of Wood by Raman SpectroscopyThe degree of carbonization of; the demonstration of g-C by XRD3N4The composition with wood is successful; the experimental results show that g-C3N4@ wood photodegradation rate of MB reaches 96.02% within 60 minutes; the efficiency can still reach 80% after 5 times of recycling.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 shows g-C prepared in example 1 of the present invention3N4SEM (b), TEM image (c) of @ wood composite;
FIG. 2 shows g-C prepared in example 1 of the present invention3N4g-C of @ wood composite material3N4@ wood composite material N2Adsorption/desorption isotherms (a) and corresponding pore size profiles (b);
FIG. 3 shows g-C prepared in example 1 of the present invention3N4The XRD spectrum (a) and Raman spectrum (b) of the @ wood composite material;
FIG. 4(a) is a hierarchical porous g-C prepared in example 1 from Methylene Blue (MB) solution (10 mg/L)3N4The change in the UV-visible absorption spectrum in the presence of @ wood composite (10 mg); (b) is the rate of change of the concentration ratio of the MB solution with time; (c) is the change of the photocatalytic degradation rate of MB with time; (d) hierarchical porous g-C prepared for example 13N4@ wood composite degradation rate in the first 5 cycles within 60 minutes.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and washing; the cutting method is a handsaw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an acid solution, and drying to obtain a wood strip precursor, wherein the acid solution is a hydrochloric acid solution, the concentration of the acid solution is 1 mol/L, the stirring and soaking time in the acid solution is 3 days, the stirring speed of the stirring and soaking is 400r/min, the using amount of the wood strips is 500m L, and 8 wood strips with the size of 3x2x1cm are added into the acid solution;
step three, stirring and soaking the batten precursor in a melamine solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into a new melamine solution, stirring, soaking and drying the batten precursor until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the melamine solution is 5 wt%, the stirring and soaking temperature in the melamine solution is 90 ℃, the stirring and soaking time is 1h, and the stirring speed for stirring and soaking is 400r/min, and the dosage of the batten precursor is that 2 batten precursors with the size of 3x2x1cm are added into 200m L melamine solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 200 ℃, the pre-carbonization time is 2 hours, and the gas flow rate is 100m L/min, the final carbonization temperature is 500 ℃, the final carbonization time is 5 hours, and the gas flow rate is 100m L/min, the inert gases are argon, and the nitrogen-containing gases are ammonia gases;
figure 1 shows the present inventionThe invention relates to a prepared grading porous g-C for photocatalytic degradation3N4SEM (b) and tem (c) images of @ wood composite, where fig. 1(a) is an SEM image of wood-derived carbon (WDC) obtained after direct carbonization of the batten precursor obtained in step two; the longitudinal cross-sectional SEM image of WDC (fig. 1a) clearly shows the hierarchical pore structure with ordered connectivity inside, i.e. internal cross-linking of large channels and bridging of small channels; g-C3N4SEM of @ Wood composite (FIG. 1b) shows the macroporous structure of the sample and g-C3N4An existing form attached to the WDC; g-C3N4TEM images of @ wood composites (FIG. 1c) further confirmed the tight bond between the two.
FIG. 2 shows a hierarchical porous g-C prepared according to the present invention for photocatalytic degradation3N4@ wood composite material N2Adsorption/desorption isotherms (a) and corresponding pore size profiles (b) by studying N2Adsorption/desorption isotherms to further demonstrate the presence of a hierarchical porous structure in the sample; g-C3N4@ Wood composite has a typical type I isotherm characteristic (FIG. 2a) with a BET specific surface area of 1064.39m2(ii)/g; at a lower relative pressure (p/p)00-0.1) sharp temperature rise corresponding to abundant micropores, typical H4 hysteresis loop (p/p) appears at medium pressure00.4 to 0.9) indicates the presence of a large number of mesopores; FIG. 2b shows the pore size distribution in the range of 0nm to 50nm, on the basis of which g-C is calculated by the JBH method3N4The micropore and mesopore size of @ wood composite is shown in the table in figure 2 b; thus, the discussion in connection with SEM is illustrative of g-C prepared by the present method3N4The @ wood composite material has an ordered hierarchical porous structure of micropores, mesopores and macropores.
FIG. 3 shows a graded porous g-C prepared according to the invention for photocatalytic degradation3N4The XRD spectrum (a) and Raman spectrum (b) of the @ wood composite material; the carbonization degree of wood is characterized by Raman spectrum; the demonstration of g-C by XRD3N4The composition with wood is successful; the prepared WDC, g-C were analyzed by XRD3N4And g-C3N4The crystal structure of @ wood composite (figure 3 a); the two broad peaks at 24.3 ° and 43.1 ° are caused by the typical (002) and (111) crystal planes of graphitized wood, while g-C3N4Are (100) and (002) crystal planes at 12.9 ° and 27.5 °, respectively (JCPDS 87-1526); furthermore, after pyrolysis of the melamine-containing wood, a combination with g-C was observed at 27.5 °3N4(002) reflects a corresponding new diffraction peak, indicating g-C3N4Successful introduction of (1); in order to characterize the degree of graphitization after pyrolysis of wood, its vibrational behavior was studied using raman spectroscopy (fig. 3 b); g belt (located at 1598 cm)-1D band (at 1365 cm) due to graphite in-plane vibration-1And) is generally considered to be associated with a double resonance raman process in disordered carbons. Intensity ratio of G band and D band in carbon material (I)G/ID) Typically representing the degree of graphitization. Determination of WDC and g-C3N4@ Wood composite Material IG/IDThe values reached 1.170 and 1.145, respectively. g-C compared with WDC3N4The relatively low values of @ wood composites may be caused by melamine reducing or causing defects in the graphitization of natural wood.
Example 2:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and washing; the cutting method is a handsaw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an acid solution, and drying to obtain a wood strip precursor, wherein the acid solution is a hydrochloric acid solution, the concentration of the acid solution is 0.5 mol/L, the stirring and soaking time in the acid solution is 3 days, the stirring speed of the stirring and soaking is 400r/min, and the using amount of the wood strips is that 10 wood strips with the size of 3x2x1cm are added into 500m L acid solution;
step three, stirring and soaking the batten precursor in a melamine solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into a new melamine solution, stirring and soaking, and then drying until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the melamine solution is 8 wt%, the stirring and soaking temperature in the melamine solution is 90 ℃, the stirring and soaking time is 0.5h, and the stirring speed in the stirring and soaking process is 400r/min, and the dosage of the batten precursor is 200m L, 2 batten precursors with the size of 3x2x1cm are added into the melamine solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 200 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 600 ℃, the final carbonization time is 6 hours, the gas flow rate is 100m L/min, the inert gases are argon, and the nitrogen-containing gases are ammonia.
Example 3:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and ethanol washing; the cutting method is an electric saw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an alkaline solution for 3 days, and then drying to obtain a wood strip precursor, wherein the alkaline solution is a sodium hydroxide solution, the concentration of the alkaline solution is 1 mol/L, the stirring and soaking speed of the stirring and soaking is 400r/min, and the using amount of the wood strips is that 10 wood strips with the size of 3x2x1cm are added into 500m L alkaline solution;
step three, stirring and soaking the batten precursor in a melamine solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into a new melamine solution, stirring, soaking and drying the batten precursor until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the melamine solution is 10 wt%, the stirring and soaking temperature in the melamine solution is 90 ℃, the stirring and soaking time is 0.5h, and the stirring speed for stirring and soaking is 400r/min, and the dosage of the batten precursor is 200m L, 2 batten precursors with the size of 3x2x1cm are added into the melamine solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 250 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 650 ℃, the final carbonization time is 5 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
Example 4:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and ethanol washing; the cutting method is an electric saw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an alkaline solution for 3 days, and then drying to obtain a wood strip precursor, wherein the alkaline solution is a sodium hydroxide solution, the concentration of the alkaline solution is 1 mol/L, the stirring and soaking speed of the stirring and soaking is 400r/min, and the using amount of the wood strips is that 10 wood strips with the size of 3x2x1cm are added into 500m L alkaline solution;
step three, stirring and soaking the wood bar precursor in a urea solution, taking out and drying the wood bar precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried wood bar precursor into a new urea solution for stirring and soaking, and then drying until white particles are uniformly attached to the surface of the wood bar precursor, wherein the mass fraction of the urea solution is 15 wt%, the stirring and soaking temperature in the urea solution is 35 ℃, the stirring and soaking time is 0.5h, and the stirring speed for stirring and soaking is 400r/min, wherein the dosage of the wood bar precursor is 200m L, and 2 wood bar precursors with the size of 3x2x1cm are added into the urea solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 250 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 580 ℃, the final carbonization time is 5 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
Example 5:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and ethanol washing; the cutting method is an electric saw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an alkaline solution for 3 days, and then drying to obtain a wood strip precursor, wherein the alkaline solution is a sodium hydroxide solution, the concentration of the alkaline solution is 1 mol/L, the stirring and soaking speed of the stirring and soaking is 400r/min, and the using amount of the wood strips is that 10 wood strips with the size of 3x2x1cm are added into 500m L alkaline solution;
step three, stirring and soaking the batten precursor in thiourea solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into new thiourea solution, stirring and soaking, and then drying until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the thiourea solution is 12 wt%, the stirring and soaking temperature in the thiourea solution is 35 ℃, the stirring and soaking time is 0.5h, and the stirring speed for stirring and soaking is 400r/min, and the dosage of the batten precursor is that 2 batten precursors with the size of 3x2x1cm are added into 200m L thiourea solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 250 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 600 ℃, the final carbonization time is 5 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
Example 6:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and washing; the cutting method is a handsaw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an acid solution, and drying to obtain a wood strip precursor, wherein the acid solution is a hydrochloric acid solution, the concentration of the acid solution is 1 mol/L, the stirring and soaking time in the acid solution is 3 days, the stirring speed of the stirring and soaking is 400r/min, the using amount of the wood strips is 500m L, and 8 wood strips with the size of 3x2x1cm are added into the acid solution;
step three, stirring and soaking the batten precursor in a melamine solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into a new melamine solution, stirring, soaking and drying the batten precursor until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the melamine solution is 5 wt%, the stirring and soaking temperature in the melamine solution is 90 ℃, the stirring and soaking time is 1h, and the stirring speed for stirring and soaking is 400r/min, and the dosage of the batten precursor is that 2 batten precursors with the size of 3x2x1cm are added into 200m L melamine solution;
step four, directly carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The method comprises the following steps of @ wood composite material, wherein direct carbonization is carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gas adopted by the atmosphere furnace is inert gas and/or nitrogen-containing gas, the direct carbonization temperature is 550 ℃, the time is 12 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
Example 7:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and washing; the cutting method is a handsaw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an acid solution, drying to obtain a wood strip precursor, putting the wood strip precursor into a supercritical device, soaking for 30min in a supercritical acetone-water system with the temperature of 360 ℃ and the pressure of 12MPa, and drying to obtain a treated wood strip precursor, putting the treated wood strip precursor into a reaction cavity of low-temperature plasma, vacuumizing until the pressure in the reaction cavity is stable, introducing a reaction gas containing ammonia, performing surface treatment on the wood strip precursor through low-temperature plasma discharge to obtain the treated wood strip precursor, modifying the surface of the wood strip precursor through soaking of the supercritical acetone-water system and treatment of the low-temperature plasma, further improving the combination of the wood strip precursor and the nitrogen-containing precursor solution, wherein the acid solution is a hydrochloric acid solution, the concentration of the acid solution is 1 mol/L, the stirring and soaking time in the acid solution is 3 days, the stirring and soaking speed of the stirring is 400r/min, the dosage of the wood strips is 500m L, the size of the blocks is 3x 2min, the mixing pressure of the ammonia in the acetone-water system is 636 Pa, and the acetone-water is a mixing ratio of the ammonia to the acetone gas of the acetone-water system is 20W 4;
step three, stirring and soaking the batten precursor in a melamine solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into a new melamine solution, stirring, soaking and drying the batten precursor until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the melamine solution is 5 wt%, the stirring and soaking temperature in the melamine solution is 90 ℃, the stirring and soaking time is 1h, and the stirring speed for stirring and soaking is 400r/min, and the dosage of the batten precursor is that 2 batten precursors with the size of 3x2x1cm are added into 200m L melamine solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4@ wood composite materials; the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace; the atmosphere furnace isThe method comprises the steps of preparing a vertical furnace, wherein the gas adopted by the atmosphere furnace is inert gas and nitrogen-containing gas, the pre-carbonization temperature is 200 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 500 ℃, the final carbonization time is 5 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
Example 8:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and ethanol washing; the cutting method is an electric saw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an alkaline solution, and drying to obtain a wood strip precursor, putting the wood strip precursor into a supercritical device, soaking the wood strip precursor in a supercritical acetone-water system with the temperature of 360 ℃ and the pressure of 12MPa for 30min, and drying to obtain a treated wood strip precursor, putting the treated wood strip precursor into a reaction cavity of low-temperature plasma, vacuumizing until the pressure in the reaction cavity is stable, introducing a reaction gas containing ammonia, and performing surface treatment on the wood strip precursor through low-temperature plasma discharge to obtain the treated wood strip precursor, wherein the alkaline solution is a sodium hydroxide solution, the concentration of the alkaline solution is 1 mol/L, the stirring and soaking time in the alkaline solution is 3 days, the stirring speed of the stirring and soaking is 400r/min, the amount of the wood strips is 500m L, 10 wood strips with the size of 3x2x1cm are added into the alkaline solution, the volume ratio of acetone to water in the supercritical acetone-water system is 4:1, the reaction gas containing argon is mixed with the reaction gas, and the ammonia discharge power is 15Pa of the plasma;
step three, stirring and soaking the wood bar precursor in a urea solution, taking out and drying the wood bar precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried wood bar precursor into a new urea solution for stirring and soaking, and then drying until white particles are uniformly attached to the surface of the wood bar precursor, wherein the mass fraction of the urea solution is 15 wt%, the stirring and soaking temperature in the urea solution is 35 ℃, the stirring and soaking time is 0.5h, and the stirring speed for stirring and soaking is 400r/min, wherein the dosage of the wood bar precursor is 200m L, and 2 wood bar precursors with the size of 3x2x1cm are added into the urea solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 250 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 580 ℃, the final carbonization time is 5 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
Example 9:
hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material comprises the following steps:
firstly, selecting basswood, removing surface pollutants, and cutting the basswood into wood strips; the method for removing the surface pollutants comprises surface scratching and ethanol washing; the cutting method is an electric saw; the size of the wood strip is 3x2x1 cm;
repeatedly washing the wood strips, stirring and soaking the wood strips in an alkaline solution, drying to obtain a wood strip precursor, putting the wood strip precursor into a supercritical device, soaking the wood strip precursor in a supercritical acetone-water system at the temperature of 370 ℃ and the pressure of 10MPa for 30min, and drying to obtain a treated wood strip precursor, putting the treated wood strip precursor into a reaction cavity of low-temperature plasma, vacuumizing until the pressure in the reaction cavity is stable, introducing a reaction gas containing ammonia, performing surface treatment on the wood strip precursor through low-temperature plasma discharge to obtain the treated wood strip precursor, wherein the volume ratio of acetone to water in the supercritical acetone-water system is 4:1, the reaction gas containing ammonia is a mixed gas of ammonia and argon, the power during low-temperature plasma discharge treatment is 60W, the pressure is 25Pa, the time is 5min, the alkaline solution is a sodium hydroxide solution, the concentration of the alkaline solution is 1 mol/L, the stirring and soaking time in the alkaline solution is 3 days, the stirring speed of the stirring and soaking is 400r/min, and the dosage of the wood strips in the alkaline solution is 362 x 2;
step three, stirring and soaking the batten precursor in thiourea solution, taking out and drying the batten precursor, and repeating the soaking and drying processes for 3 times, namely adding the dried batten precursor into new thiourea solution, stirring and soaking, and then drying until white particles are uniformly attached to the surface of the batten precursor, wherein the mass fraction of the thiourea solution is 12 wt%, the stirring and soaking temperature in the thiourea solution is 35 ℃, the stirring and soaking time is 0.5h, and the stirring speed for stirring and soaking is 400r/min, and the dosage of the batten precursor is that 2 batten precursors with the size of 3x2x1cm are added into 200m L thiourea solution;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, finally carbonizing, cooling to room temperature, and taking out a solid, namely the graded porous g-C for photocatalytic degradation3N4The wood composite material is prepared by the following steps of @, wherein the pre-carbonization and the final carbonization are both carried out in an atmosphere furnace, the atmosphere furnace is a vertical furnace, gases adopted by the atmosphere furnace are inert gases and nitrogen-containing gases, the pre-carbonization temperature is 250 ℃, the pre-carbonization time is 2 hours, the gas flow rate is 100m L/min, the final carbonization temperature is 600 ℃, the final carbonization time is 5 hours, the gas flow rate is 100m L/min, the inert gas is argon, and the nitrogen-containing gas is ammonia.
The graded porous g-C prepared in example 1 was investigated by degrading wastewater containing Methylene Blue (MB)3N4@ Wood composite Material (g-C)3N4@ WDC); the specific experimental process is as follows: grading the porous g-C3N4@ Wood composite 10mg was added to MB solution of 50m L10 mg/L, the mixture was stirred in the dark for 30 minutes before photocatalytic reaction to obtain adsorption-deposition equilibrium, and then the solution was transferred to a photocatalytic reactor using a xenon lamp (300w, lambda)>400nm) is irradiated on the solution for 60min, at the time of 5, 10, 20, 30, 40, 50 and 60min, the reaction solution 3m L is taken out from a centrifuge tube and centrifuged at 10000r/min for 2min, the supernatant is taken, the concentration of the solution is measured by an ultraviolet spectrophotometer, for the recycling experiment, after one experiment is finished, the steps are repeated for the next experiment for separating and grading the porous g-C3N4@ wood composite material, and the result is shown in figure 4, wherein (a) is Methylene Blue (MB) solution (10 mg/L) in the porous g-C3N4@ wood composite material3N4The change in the UV-visible absorption spectrum in the presence of @ wood composite (10 mg); (b) for the rate of change of the concentration ratio of the MB solution over time calculated from (a), Blank (Blank control group) demonstrated that no g-C was added3N4The MB solution concentration ratio is unchanged within 60min when @ WDC samples are taken; the pure wood derived carbon WDC (namely, the product obtained by directly carbonizing the batten precursor obtained in the step two) does not have the photodegradation capability per se; (c) is the change of the photocatalytic degradation rate of MB with time; (d) to classify porous g-C3N4@ wood composite the degradation rate of MB solution in the first 5 cycles.
The graded porous g-C prepared in examples 1, 4, 5 and 7-9 were investigated by degrading wastewater containing Methylene Blue (MB)3N4@ photocatalytic activity of wood composites; the specific experimental process is as follows: grading the porous g-C3N4@ Wood composite 10mg was added to MB solution of 50m L10 mg/L, the mixture was stirred in the dark for 30 minutes before photocatalytic reaction to obtain adsorption-deposition equilibrium, and then the solution was transferred to a photocatalytic reactor using a xenon lamp (300w, lambda)>400nm) irradiating the solution for 60min, centrifuging the reaction solution 3m L in a centrifuge tube at 10000r/min for 2min at 60min, collecting the supernatant, measuring the concentration of the solution with an ultraviolet spectrophotometer, performing 3 times of repeated experiments in each example, averaging the results, performing cyclic utilization experiments, and separating after one experimentHierarchical porous g-C3N4The @ wood composite material is subjected to the next experiment by repeating the steps, and the degradation rate of the composite material to MB after the fifth cycle is tested; the degradation rate for MB is shown in table 1;
TABLE 1
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (10)
1. Hierarchical porous g-C for photocatalytic degradation3N4The preparation method of the @ wood composite material is characterized by comprising the following steps of:
firstly, selecting waste natural wood, removing surface pollutants, and cutting the waste natural wood into battens;
repeatedly washing the batten, stirring and soaking the batten in an acidic or alkaline solution, and drying to obtain a batten precursor;
step three, stirring and soaking the batten precursor in a nitrogen-containing precursor solution, and then taking out and drying the batten precursor; repeating the soaking and drying processes for 3-5 times until white particles are uniformly attached to the surface of the batten precursor;
step four, pre-carbonizing the batten precursor with white particles uniformly attached to the surface obtained in the step three, then finally carbonizing, cooling to room temperature, and taking out solids, namely the graded porous g-C for photocatalytic degradation3N4@ wood composite material.
2. The graded porous g-C for photocatalytic degradation as claimed in claim 13N4@ wood composite materialThe preparation method is characterized in that the waste natural wood comprises but is not limited to any one of basswood, bamboo, walnut, sapellia, cherry and maple wood; in the first step, the method for removing the surface pollutants comprises one or a combination of more of surface scratching, water washing, ethanol washing, acid washing and alkali washing; the cutting method is any one of hand saw, electric saw, laser cutting and electric cutting; the shape of the wood strip is any one of square, rectangle, sphere and ellipse; the acid washing adopts one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid and silicic acid as a reagent; the alkaline washing reagent is one or a combination of sodium hydroxide, potassium hydroxide, ammonia water and ammonia monohydrate; the drying mode is as follows: natural air drying, freeze drying, supercritical drying, constant temperature heating drying, and variable temperature heating drying.
3. The graded porous g-C for photocatalytic degradation as claimed in claim 13N4The preparation method of the @ wood composite material is characterized in that in the second step, the acidic solution is one or a mixture of more of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, an acetic acid solution, a carbonic acid solution and a silicic acid solution, the alkaline solution is one or a combination of more of a sodium hydroxide solution, a potassium hydroxide solution, an ammonia water solution and an ammonia monohydrate solution, the concentration of the acidic solution is 0.5-1.5 mol/L, the concentration of the alkaline solution is 0.5-1.5 mol/L, the stirring and soaking time in the acidic or alkaline solution is 3-5 days, and the stirring speed of the stirring and soaking is 300-400 r/min.
4. The graded porous g-C for photocatalytic degradation as claimed in claim 33N4The preparation method of the @ wood composite material is characterized in that in the second step, 5-10 pieces of battens with the size of 3x2x1cm are added into 500m of L acidic solution or alkaline solution.
5. The light of claim 1Catalytic degradation of graded porous g-C3N4The preparation method of the @ wood composite material is characterized in that the nitrogen-containing precursor solution is any one of melamine solution, urea solution and thiourea solution, the mass fraction of the nitrogen-containing precursor solution is 0.1-20 wt%, the temperature for stirring and soaking in the nitrogen-containing precursor solution is 10-100 ℃, the stirring and soaking time is 0.1-3 h, the stirring speed for stirring and soaking is 300-400 r/min, and the amount of the batten precursor is that 1-2 batten precursors with the size of 3x2x1cm are added into every 200m L of the nitrogen-containing precursor solution.
6. The graded porous g-C for photocatalytic degradation as claimed in claim 13N4The preparation method of the @ wood composite material is characterized in that the pre-carbonization and the final carbonization are carried out in an atmosphere furnace, the atmosphere furnace is any one of a vertical furnace, a horizontal furnace and a tubular furnace, the gas adopted by the atmosphere furnace is inert gas and/or nitrogen-containing gas, the pre-carbonization temperature is 100-400 ℃, the pre-carbonization time is 0.1-5 hours, the gas flow rate is 1-200 m L/min, the final carbonization temperature is 400-800 ℃, the final carbonization time is 0.1-30 hours, and the gas flow rate is 1-200 m L/min.
7. The graded porous g-C for photocatalytic degradation as claimed in claim 13N4The preparation method of the @ wood composite material is characterized in that in the fourth step, the batten precursor with white particles uniformly attached to the surface, obtained in the third step, is directly carbonized, cooled to room temperature, and the solid, namely the graded porous g-C for photocatalytic degradation is taken out3N4The method comprises the following steps of @ wood composite material, wherein direct carbonization is carried out in an atmosphere furnace, the atmosphere furnace is any one of a vertical furnace, a horizontal furnace and a tubular furnace, gas adopted by the atmosphere furnace is inert gas and/or nitrogen-containing gas, the direct carbonization temperature is 400-800 ℃, the time is 1-30 hours, and the gas flow rate is 1-200 m L/min.
8. The method according to claim 6 or 7 for photocatalysisDegradable graded porous g-C3N4The preparation method of the @ wood composite material is characterized in that the inert gas is any one of argon and nitrogen; the nitrogen-containing gas is ammonia gas.
9. The graded porous g-C for photocatalytic degradation as claimed in claim 13N4The preparation method of the @ wood composite material is characterized by further comprising the following steps of: putting the batten precursor into a supercritical device, soaking for 10-30 min in a supercritical acetone-water system with the temperature of 350-370 ℃ and the pressure of 10-15 MPa, and drying to obtain a treated batten precursor; and placing the treated batten precursor into a reaction cavity of low-temperature plasma, vacuumizing until the pressure in the cavity is stable, introducing reaction gas containing ammonia, and performing surface treatment on the batten precursor through low-temperature plasma discharge to obtain the treated batten precursor.
10. The graded porous g-C for photocatalytic degradation as claimed in claim 93N4The preparation method of the @ wood composite material is characterized in that the volume ratio of acetone to water in the supercritical acetone-water system is 4: 1; the reaction gas containing ammonia gas is ammonia gas or mixed gas of ammonia gas and argon gas, the power during low-temperature plasma discharge treatment is 30-100W, the pressure is 15-25 Pa, and the time is 5-8 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010372279.1A CN111389448B (en) | 2020-05-06 | 2020-05-06 | Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010372279.1A CN111389448B (en) | 2020-05-06 | 2020-05-06 | Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111389448A true CN111389448A (en) | 2020-07-10 |
| CN111389448B CN111389448B (en) | 2022-01-28 |
Family
ID=71418468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010372279.1A Active CN111389448B (en) | 2020-05-06 | 2020-05-06 | Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111389448B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023973A (en) * | 2020-09-10 | 2020-12-04 | 北京科技大学 | g-C with high photocatalytic efficiency3N4And method for preparing the same |
| CN112962114A (en) * | 2021-02-03 | 2021-06-15 | 西北工业大学深圳研究院 | Photocatalytic full-hydrolysis/fuel cell integrated system and preparation method |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118726A1 (en) * | 2004-06-04 | 2005-12-15 | Sto Ag | Coating composition |
| CN101362827A (en) * | 2008-09-26 | 2009-02-11 | 复旦大学 | Method for processing cellulose by supercritical carbon dioxide, products and use thereof |
| CN102702807A (en) * | 2012-06-14 | 2012-10-03 | 金华氟特催化科技有限公司 | Photo-catalytic composite coating and preparation method thereof |
| CN104136579A (en) * | 2011-11-03 | 2014-11-05 | 索拉瑞控股有限公司 | Method for removal of toxic waste from timber |
| CN104128171A (en) * | 2014-07-02 | 2014-11-05 | 昆明理工大学 | Titanium-dioxide charcoal composite material and preparation method thereof |
| CN104525234A (en) * | 2014-12-17 | 2015-04-22 | 上海交通大学 | Preparation method for graphite-phase carbon nitride photocatalytic material |
| CN104801246A (en) * | 2015-04-09 | 2015-07-29 | 西南科技大学 | Preparation method for mycelium nano composite pellet of core-shell structure |
| CN105344370A (en) * | 2015-11-30 | 2016-02-24 | 中南大学 | Porous carbon nitride/copper sulfide photocatalytic composite material with p-n structure and preparation method thereof |
| CN108855195A (en) * | 2018-08-07 | 2018-11-23 | 深圳大学 | A kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method |
| CN110564098A (en) * | 2019-07-29 | 2019-12-13 | 河北晨阳工贸集团有限公司 | nano lignocellulose/graphite-like phase carbon nitride composite material, woodware coating, preparation method and application |
| CN110732319A (en) * | 2019-10-31 | 2020-01-31 | 内蒙古农业大学 | wood activated carbon body-loaded titanium dioxide material and preparation method and application thereof |
| CN110743497A (en) * | 2019-10-28 | 2020-02-04 | 西南科技大学 | Preparation method of bionic structure ultra-light carbon aerogel |
-
2020
- 2020-05-06 CN CN202010372279.1A patent/CN111389448B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118726A1 (en) * | 2004-06-04 | 2005-12-15 | Sto Ag | Coating composition |
| CN101362827A (en) * | 2008-09-26 | 2009-02-11 | 复旦大学 | Method for processing cellulose by supercritical carbon dioxide, products and use thereof |
| CN104136579A (en) * | 2011-11-03 | 2014-11-05 | 索拉瑞控股有限公司 | Method for removal of toxic waste from timber |
| CN102702807A (en) * | 2012-06-14 | 2012-10-03 | 金华氟特催化科技有限公司 | Photo-catalytic composite coating and preparation method thereof |
| CN104128171A (en) * | 2014-07-02 | 2014-11-05 | 昆明理工大学 | Titanium-dioxide charcoal composite material and preparation method thereof |
| CN104525234A (en) * | 2014-12-17 | 2015-04-22 | 上海交通大学 | Preparation method for graphite-phase carbon nitride photocatalytic material |
| CN104801246A (en) * | 2015-04-09 | 2015-07-29 | 西南科技大学 | Preparation method for mycelium nano composite pellet of core-shell structure |
| CN105344370A (en) * | 2015-11-30 | 2016-02-24 | 中南大学 | Porous carbon nitride/copper sulfide photocatalytic composite material with p-n structure and preparation method thereof |
| CN108855195A (en) * | 2018-08-07 | 2018-11-23 | 深圳大学 | A kind of carbon doping amorphous carbon nitride photochemical catalyst and preparation method |
| CN110564098A (en) * | 2019-07-29 | 2019-12-13 | 河北晨阳工贸集团有限公司 | nano lignocellulose/graphite-like phase carbon nitride composite material, woodware coating, preparation method and application |
| CN110743497A (en) * | 2019-10-28 | 2020-02-04 | 西南科技大学 | Preparation method of bionic structure ultra-light carbon aerogel |
| CN110732319A (en) * | 2019-10-31 | 2020-01-31 | 内蒙古农业大学 | wood activated carbon body-loaded titanium dioxide material and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| DONG, YUE ET AL: "A self-cleaning surface based on heat treatment of g-C3N4-coated wood prepared by a rapid and eco-friendly method", 《HOLZFORSCHUNG》 * |
| LINZHEN WU ET AL: "Functionally integrated g-C3N4@wood-derived carbon with an orderly interconnected porous structure", 《APPLIED SURFACE SCIENCE》 * |
| MA, SHUAISHUAI ET AL: "Facile Synthesis of Carbon/g-C3N4 Nanocomposites as Metal-Free Photocatalyst with Enhanced Visible-Light-Responsive Photocatalytic Properties", 《CHEMISTRYSELECT》 * |
| 董悦: "基于类石墨相氮化碳改性木材表面疏水和光催化性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
| 袁炳楠 等: "木材表面g-C3N4的固定及其光降解性能表征", 《南京林业大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023973A (en) * | 2020-09-10 | 2020-12-04 | 北京科技大学 | g-C with high photocatalytic efficiency3N4And method for preparing the same |
| CN112962114A (en) * | 2021-02-03 | 2021-06-15 | 西北工业大学深圳研究院 | Photocatalytic full-hydrolysis/fuel cell integrated system and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111389448B (en) | 2022-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112898515B (en) | Preparation method of porous covalent organic framework material with triazine structure | |
| CN111389448B (en) | Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material | |
| CN115043479B (en) | Nitrogen-doped biochar as well as preparation method and application thereof | |
| CN109395763B (en) | Sulfur-doped g-C3N4C-dot porous composite photocatalyst and preparation method and application thereof | |
| CN110270305B (en) | Application of scaly transition metal sulfide carbon nano material | |
| CN113318764A (en) | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst | |
| CN112897525A (en) | For capturing CO2Preparation method of nitrogen-rich carbon material | |
| CN110756168A (en) | Preparation method and application of modified biochar for adsorbing tetracycline in wastewater | |
| CN103252214A (en) | Active carbon fiber and graded porous Ni-Ni3P/active carbon fiber composite material as well as preparation and application of two | |
| CN108176355B (en) | Multilayer macroporous-mesoporous-microporous polymer derivative ceramic adsorption material and preparation method thereof | |
| CN113842884A (en) | Medium-temperature hydrophobic decarbonization adsorbent and preparation method thereof | |
| CN111068622A (en) | Porous adsorption material and preparation method thereof | |
| CN114797766A (en) | Porous biochar and preparation method and application thereof | |
| Shuahua et al. | The comparison of different activation techniques to prepare activated carbon materials from waste cotton fabric | |
| CN111744523A (en) | Nitrogen-doped carbon nanosheet, and preparation method and application thereof | |
| CN115536022A (en) | Biomass porous carbon material based on mangosteen shells and preparation method thereof | |
| CN108862277A (en) | Rice husk-sludge base composite activated carbon and preparation method thereof | |
| KR102544657B1 (en) | The Method of Producing Active Carbon by Using Physical Activation and the Active Carbon Produced by the Same | |
| Li et al. | Rapid preparation of porous carbon by Flash Joule heating from bituminous coal and its adsorption mechanism of methylene blue | |
| CN114560717A (en) | Preparation method and application of one-dimensional porous boron nitride fiber material | |
| CN112142032A (en) | Porous charcoal containing three-dimensional amorphous carbon framework and preparation method and application thereof | |
| CN114956040B (en) | Nitrogen-oxygen doped hierarchical porous carbon material, preparation method and application | |
| CN113428854B (en) | For CO 2 Adsorbed wood-based porous carbon materials and methods of making the same | |
| Quyen et al. | A simple and rapid preparation of activated carbons with highly surface area from durian shell ash | |
| CN112723334B (en) | Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |